Spirobi (meta-dioxane) derivatives containing sulfur and halogen



United States Patent-*- 2,992,233 SPIROBIGWETA-DIOXANE) DERIVATIVES CON- TAINING SULFUR AND HALOGEN HarryA. Stansbury, Jr., South Charleston, and Howard R. Guest, Charleston, W. Va., assignors to Union Carbide Corporation, a corporation of New York No Drawing. Filed Sept. 26, 1957, Ser. No. 686,276 9 Claims. (CL 260340.7)

This invention relates to novel spirobi(metadioxane) derivatives and their preparation. Ina particular aspect, this invention relates to the production of sulfurand halogen-containing spirobi(meta dioxane) derivatives which are useful as intermediate reactants and as accelerators for curing rubber.

It is an object of the present invention to provide a method for producing sulfurand halogen-containing spirobi(meta-dioxane) derivatives from 3,9-divinylspirobi- (meta-dioxane) compounds.

It is another object of this invention to provide sulfurand halogen-containing spirobi(meta-dioxane) derivatives which have active sites that can react under suitable conditions.

Other objects and advantages of the present invention will become apparent to those skilled in the art from the following description.

The compounds according to this invention are produced by reacting together a 3,9-divinylspirobi(meta-dioxane) derivative and a sulfur halide having at least one reactive (SX) group, wherein X is a halogen with an atomic weight between 30 and 130, i.e., chlorine, bromine and iodine.

The 3,9-divinylspirobi(meta-dioxane) reactants preferred are those which have the formula:

00132 011 0 D-C O HC-D wherein D is selected from the group consisting of (R-CH=CH) (Cal) and stituted on the vinyl groups are generally more difilcult to prepare. These other groups must be of a character and in a position on the vinylgroups not to interfere with the effective reactions of 3,9-divinylspirobi(meta-dioxane) compounds in the processes of the present invention.

3,9 divinyl-spirobi(meta dioxane) compounds which contain a terminal methylene group are of particular advantage for ease of reaction, quality of product, etc. Their use, therefore, generally is the most preferred. Substituents on the vinyl groups of a spirobi(meta-dioxane) nucleus may be included to alter the properties of the reaction product and/ or to act as reactive sites for chemical transformation of said products under suitable conditions.

The preferred 3,9-divinylspirobi(meta-dioxane) starting materials of this present invention may be prepared by the condensation of a mole of pentaerythritol with two moles of acrolein or an acrolein derivative in the presence of an acid catalyst such as p-toluenesulfonie 2,992,233 Patented July 11, 1961 ice HOCH: CHgOH OH OHCHOH-l- C 11+ 2 I:

g HOG 2 CHrOH OCH: CHzO CH =OHC O CHCH= CHg+2H1O 0C a C 20 When the condensation is conducted with (a) alphamethyl acrolein, or (b) crotonaldehyde, then methyl-substituted 3,9-divinylspirobi (meta-dioxanes) are obtained:

CH: HOCHa CHaOH 2OHF= CHO+ G g H0O I CHiOH OH; OCH: CHgO CH C 2= 0 a 2 10 H 8 C CH CH-l-H 0C 1 CHiO HOOH: CHaOH 2CHiOH=CHCHO+ C\ HOCz CHiOH OCH: CH:|O\ OH|CH=CHO O CHCH=CHCH;+2H|O It is not necessary that the 0:,fl-IJDS8tUI3tCd aldehyde reacted with pentaerythritol be pure or a single species. Mixtures of c p-unsaturated aldehydes may be condensed with pentaerythritol for purposes of convenience and economy. The resulting products are mixtures of 3,9- divinylspirobi(meta-dioxane) compounds which may be used in their crude form directly in the processes of this invention.

As previously mentioned, in the processes of this invention novel chemical compounds are produced by reacting a 3,9-divinylspirobi(meta-dioxane) derivative with a sulfur halide containing at least one reactive (SX) group, where X is a halogen with an atomic weight between 30 and 130, i.e., chlorine, bromine and iodine. The term sulfur halide as used in this invention is meant to include both inorganic sulfur halides and organic sulfenyl halides.

The sulfur halide reactants preferred are those which have the formula:

- this invention is the presence of at least one sulfur-halogen group (SX) which is capable of splitting into sulfur and halogen radicals, said radicals then having the ability to react with the vinyl positions in 3,9-divinylspirobi(meta-dioxane) compounds. Sulfur halides which are applicable for the production of the novel compounds of this invention include sulfur monochloride, sulfur dichloride, sulfur monobromide, methanesulfenyl chloride, trichloromethylsulfenyl chloride; trifluoromethanesulfenyl chloride; -monochloromethanesulfenyl chloride; dichloromethoxymethanesulfenyl chloride; triphenylmethanesulfenyl chloride; ethanesulfenyl chloride; l-chloroethane- 'sulfenyl chloride; l,l-dichloroethanesulfenyl chloride; l=chloroethanesulfenyl chloride, 2-chloroethanesulfenyl bromide, ethylenebis(disulfur chloride); ethylenebis('disulfur bromide), propanesulfenyl chloride; l-chloropropanesulfenyl chloride; 3-chloropropanesulfenyl chloride; l-ch1oro-2-propanesulfenyl chloride; l,l-dichloropropane- 'sulfenyl chloride; butanesulfenyl chloride; benzenesulfenyl chloride; p-chlorobenzenesulfenyl chloride; 2-nitrobenzenesulfenyl bromide; 2Adinitrobenzenesulfenyl bromide; Z-nitrobenzenedisulfur chloride; benzothiazolylsulfenyl chloride; benzothiazolylsulfenyl bromide; benzothiazolyliodide, and the like.

Several different methods of synthesizing sulfur halides arereportedin the chemical literature. The following reaction schemes are examples of some synthetic methods applicable for the preparation of these compounds:

(12) RCOSR'+C1 RCOCl+R'SCl RSCl+Cl, l 3) RCOSR' +Cl RCCl SCl+R'SCl A particular illustration of the methods used to produce the novel sulfurand halogen-containing compounds of this invention is the reaction of ethanesul'fenyl'bromide with 3,9-(a,a'-dimethyl-) divinylspirobi(meta-dioxane) OH, OCH, cH,o CH:

oH,cH,sBr+H,=oo v 0 1100:011,

OCH: CHzO OH; OCH: CHQO CH: c,H,soH,-i w o /CC=CH,

CH3 OCH; CHQO CHs +Br-o-B,--0o c 'HCG=C-H, 0,1158 OCH: 0 :0

0H, OCH, omo 0H, +O,H,S-OH,OQ o\ CC CH,SC,H,

Br 006, o ,0 Br 3H, OCH, 011,0 0H, +Br-CH,-(3C\ o noo-om-B,

CnHrS O C H: CHzO SCzHs I011, 005, 011,0 /oH, +o,H,s-oH,- on c Hoe-0mm Br 00 0H,o $0,135 Another .illustration is the reaction of :ethylenebis(disulfur chloride) with 3,9-('B,B'-dimethyl)divinylspirobi- (meta-'dioxane) 0 on, 03,0 =o1ssomomssc1+omon=onon o noon=onom- 0 on, o' ,0

"A variety of simple addition products may also be .obtained similar to those shown in the foregoing illustration.

wherein (R) is OCH: CHaO CH C HCCaHsCl- OCH, 0

The constitution of the novel compounds obtained by the methods of this invention varies in a manner depending on the reaction conditions, and on the kinds of reactants and their functionality. When the sulfur halide reactant contains one reactive (SX) group, then the reaction of the sulfur halide with 3,9-divinylspirobi(metadioxane) derivatives affords reaction products which result from the interaction of one spirobi(meta-dioxane) vinyl group with the sulfur halide compound and/or the interaction of both vinyl groups with said sulfur halide. As shown in the foregoing illustration of the reaction between ethanesulfenyl bromide and 3,9-(oc,a'-dimethyl)- divinylspirobi(meta-dioxane),there are two modes of addition of a sulfur halide to each vinyl group which accounts for additional isomeric forms.

Although a variety of isomeric products is possible for a particular set of reactants, it is not unequivocal that all or most of the isomers will be produced. Oftentimes, pure products, i.e., one isomeric form, or essentially pure products will be formed. This may be due to the inherent nature of the reactants (e.g., steric effects or electronic influences such as resonance and inductive effects) which favors the formation of one particular isomer over all the others, or it may be due to controlled manipulation of the reaction conditions in a manner known tolimit the latitude of a reaction course.

When a reaction product is a mixture of isomers then it can either be resolved into separate components, with the said components being used individually in applications, or the product mixture can be applied to some useful end without resolution into pure components. For convenience and economy, the unresolved product mixtures are preferred in most applications.

When the sulfur halide reactant contains at least two reactive (S--X) groups then polymerization can occur as well as simple addition. This is illustrated in the foregoing illustration of thereaction between ethylenebis(disulfur chloride) and 3,9-(B,18'-dimethyl)divinylspirobi- (meta-dioxane) Organic sulfur halides, i.e., sulfenyl halides, can be of an almost unlimited variety for the purposes of this invention, the only limitations being determined by practical considerations and the results desired in a particular application. As mentioned before, the essential requirement is the presence of at least one (S--X) group that is reactive with 3,9-divinylspirobi(meta-dioxane) compounds.

The reaction of a sulfur halide compound and a 3,9- divinylspirobi(meta-dioxane) proceeds well under moderate conditions. For most of the reactions it is only necessary to mix the reactants and maintain a reaction temperature between about 40 and 180 C., with a temperature between 80 and C. being in the preferred range. When particularly reactive compounds are being combined, then it may be necessary to use a temperature in the lower range of temperatures. For compounds that are sluggish in their reactivity it may be necessary to heat a reaction medium to a temperature above 200 C. It is practical and convenient to conduct the reactions under atmospheric pressure. If one of the components of the reaction mixture is volatile at the reaction temperature, thena closed system can be used under autogenous pressure or under an imposed pressure.

.A solvent medium may be used if convenient and desirable. In some cases a solvent will help yield optimum results, e.g., when the solvent compensates for incompatible solubility properties of thereactants. The solvents that are useful include benzene, toluene, xylene, chloroform, carbon tetrachloride, carbon disulfide, diox- 6 ane, diethyl ether of diethylene glycol, dibutyl ether, tetra- S, 106. Molecular weight calc.1260. Menzies-Wright hydrofuran, heptane and cyclohexane. method-1464. t

The molar ratio of 3,9-divinylspirobi(meta-dioxane) EXAMPLE 2 to sulfur halide compound can vary between about 1:10 I and 1;() 5, ith excess f lf h lid compound b i 5 This example illustrates the reaction between a spirobipreferred. The reaction can be conducted in either a (meta-dioxane) derivative and an inorganic disulfur halcontinuous or batchwise fashion. The reaction time is deide:

OCH: CHzO som=onc o ooH=oH,+2o1ssc1- 3,9-divlnylspirobi(meta-dioxane) sulfur monochlorlde pendent on the kind of reactants, the reaction conditions A solution of 3,9-diviny1spirobi(meta-dioxane) (42 and, in particular, on the reaction temperature. A typi- 20 grams, 0.2 mole) in benzene (84 grams) was stirred at cal reaction time would be between 0.1 hour and hours. a temperature of 25-30 C. in the same type of apparatus The products of this present invention have chemical as in Example 1 While sulfur monochloride (59 grams, and commercial application. They may be used as ac- 0.44 mole) was added over a period of minutes. The celerators for curing rubber and as intermediates in the solution was refluxed (92 C.) for 40 minutm, then the production of other chemicals. volatile components were removed at a kettle temperature The unique properties of these liquid and solid sulfurof 60 C./4 mm. A solid, colorless residue (60 grams, halogen-containing spirobi(meta-dioxane) derivatives can M.P. 75-83 C.) was recovered which had physical propbe imparted to other materials such as natural and synert-ies which approximated the product formula in the thetic polymers and elastomers by mixture or combination above reaction scheme. of the derivatives with the said materials. Analysis for C H Cl 0 S Calculated-C, 43.7; H,

Some of the products of this invention may be used 5.3; Cl, 15.7; S, 14.1. FoundC, 45.4; H, 5.9; CI, 14.7; as the flexibilizing constituents in resin-based adhesive S, 13.5. Molecular weight c-alc.-906. Menzies-Wright and potting compounds. They also find application in method-1045. the manufacture of putties and cements. Carbon blacks EXAMPLE 3 and other reinforcing pigments may be mixed with the 35 Solid products f this invention This example illustrates the reaction between a spirobi- Th presenc of reactive sites uch as halogen groups (meta'dioxane) derivative and an Organic Sulfur halide: in the derivatives makes them susceptible to cross-linking 00H, oHlo reactions such as would occur if said derivatives were 40 CHFCHC c ECOH=CH2+OWSCI treated wrth a cross-linking agent such as an alkali polysulfide. 0C CEO The following examples will serve to illustrate particuslgdivinylspirlbi(meta-mm) fif i' lar embodiments of this invention: 5 mm chloride 00H, orno EXAMPLE 1 om=ono o oo,u.o1soor,

This example illustrates the reaction between a spirobi- 00 0H:0 (meta-dioxane) derivative and an inorganic monosulfur 3-(trichloromethylmercapto-chloroethyl)-9-vlnylhalide: sprrobi(meta-dioxane) 00H, 011,0 OHs=CHO o\ go oH=oH,+0rsc1.

3,9-divinylsplrobi(meta-dloxane) sulfur dichloride 00g: /CH2O\ 00E: /CH2O CHFCHCfi o CC2H8Cl[-SOZH3OIC o ECCIHICP- s01 ocfig omo 00 2 011,0 3

A solution of 3,9-divinylspirobi(meta-dioxane) (42 A mixture of 3,9-divinylspirobi(meta-dioxane) (106 grams, 0.2 mole) in benzene (84 grams) was stirred at grams, 0.5 m and 95% trichloromethylsu y ch10- 25 C. in a glass reaction flask equipped with a stirrer, ride (215 grams, 1.1 moles) was heated at 140 C. for 2 reflux condenser and a glass feed tank. Sulfur dichloride hours in the same type of apparatus as in the previous (45 grams, 0.44 mole) was added to the reaction mediexamples. The reaction mixture was stripped of volatile um over a period of 30 minutes. After the mixture was components at a temperature of 124 C./8 mm. A liqheated to reflux (82 C.), the volatile components were reuid residue (191 grams) was recovered which had physi- ITIOVed at a kettle tempel'latllre 0f C-/10 to Yield cal constants which approximated the product formula f grams a tacky fesldue p l f The Product Was in the above reaction scheme, 11 1.5381. dissolved 1n hot acetone (400 milliliters) and precipitated Analysis for C H Cl O S: Calculated-C, 36.2; H,

by the addition of methanol (700 milliliters) to yield 40 41 1 3 5.7; S, 8 359; H, 4 1 333; grams of a colorless p y which s, 10.0. Molecular weight calc.--398. Menzies-Wright had physical constants that approximated the formula in 391 the above reaction scheme.

Analysis for c n cno s Calculated-C, 41.9; H, EXAMPLE 4 5.1; Cl, 22.5; S, 10.2. Found--C, 41.5; H, 5.3; CI, 22.0; This example illustrates the application of the products from Examples land 3 as effective accelerators for the vulcanization of natural rubber:

Formulations compounded 5 minutes at 75 to 90 C. on a two-roll mill Tensile, p.s.l 380 1, 300 1, 900 Elongation, percent 375 450 510 Load at'300% elongation, p. 200 600 790 'Harduess, Durometer A.-. 14 38 42 ASTM Stiffness Modulus, p.s.1 6, 300 13,000

1 Too soft and flexible for testing.

Having described our invention, we claim: 1. A composition of matter having the structure:

ane)compound-and a' sulfur halidegsaid 3,9-divinylspirobi- (meta-dioxane) having -the formula:

wherein D is selected from the group consisting of CH=CH-) and and R is selected from the group consisting of hydrogen, halogen and lower alkyl; said sulfur halide having the formula:

wherein X is halogen with atomic weight between 30 and 130; m is an integer selected from 1 and 2; and Z is selected from the groupconsisting of lower alkyl, halo lower alkyl, chlorine if X ischlorine, and bromine if X is bromine and m is 2.

5. The process of claim 4 wherein the spirobi(metadioxane) compound is 3,9-divinylspirobi(meta-dioxane).

6. The process of claim 4 wherein the spirobKmetadioxane) compound is 3,9-(u,oU-dimethyl)divinylspirobi- (meta-dioxane) 7. The process of claim 4 wherein the sulfur halide is sulfur monochloride.

8. The process of claim 4 wherein the sulfur halide is sulfur dichloride.

00E: CHgO 00g: /CH20\ CHFCHC\ /C\ HCCzHaCl --SCzHsClC C HCCzHaCl- S01 0 CH: OHIO 0 C 1 OHZO s 2. A composition of matter having the structure:

9. The process of claim 4 wherein the sulfur'halide is trichloromethylsulfenyl chloride.

00H, CHiO\ OCH: 01110 CH=GH[-C q nommot-s-s-mmtlnlo c HCCH=CE1 OCH: CHnO a OCH: CHQO 3. A composition of matter having the structure: References Cited in the file of this Patent /0 on, 01110 UNITED STATES PATENTS 'CHFQHGH 2,150,425 Cramer Mar. 14, 1939 5 2,343,566 Mathes Mar. 7, 1944 4. A process for producing halogenand sulfur-con- 2,399,068 Senkus Apr. .23, 1946 taining spirobi(meta-dioxane) derivatives which com- 2,525,681 Jones et a1. Oct. 10, .1950 prises reacting together a 3,9-divinylspirobi(meta-diox- 2,709,715 Heller May 31, 1955 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2,992,,233 July 11 1961 Y Harry A, Stansbury Jr v at al.

It is hereby certified that error appears in the above numbered pat- 1 ant requiring correction and that the said. Letters Patent should read as "corrected below.

Column 2 line 15, reading "2CH =CHCHOH+" read 2CH %;QI-lCH0 Signed and sealed this 30th day of January 1962.

(SEAL) Attest:

ERNEST W. SWIDER DAVID L. LADD Attesting Officer 7 Commissioner of Patents for that portion of the formula 

1. A COMPOSITION OF MATTER HAVING THE STRUCTURE: 